EP1398303B1 - Cerammable mineral glass, preparation of glass-ceramic articles, said articles - Google Patents
Cerammable mineral glass, preparation of glass-ceramic articles, said articles Download PDFInfo
- Publication number
- EP1398303B1 EP1398303B1 EP03292222.1A EP03292222A EP1398303B1 EP 1398303 B1 EP1398303 B1 EP 1398303B1 EP 03292222 A EP03292222 A EP 03292222A EP 1398303 B1 EP1398303 B1 EP 1398303B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- glass
- zro
- tio
- article
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
Definitions
- the present invention relates to :
- German patent application DE 199 39 787 discloses transparent, arsenic and antimony-free glass-ceramics.
- the light transmission of these glass-ceramics can be adjusted by a combination of vanadium oxide with a solid, liquid and/or gaseous reducing agent, which is added to the glass melt.
- International patent application WO 99/06334 discloses glass-ceramic plates, which are designed in particular for covering heating elements. The plates are at least 50% blurred.
- US patent 5 931 152 discloses glass-ceramic cooking plates showing a specific geometry.
- the present invention offers an improvement of said teaching.
- the characteristics of devitrification of the glass, in particular its liquidus viscosity, are critical during the second of said steps. It is known that a risk is taken of generating rejects - glass having devitrification faults, within its mass and/or on the surface - insofar as the viscosity of the glass in question is, during shaping, higher than its liquidus viscosity. Each shaping process necessitates that the glass be conditioned in a given viscosity range. A glass having a higher liquidus viscosity enables an easier shaping. The tolerance with respect to the existence of cold points is greater. This is all the more true because the volume of glass concerned is greater.
- the objects formed are in general of quite large dimensions, and, whatever the shaping technique implemented for the shaping of the precursor glasses be (lamination, pressing or shaping from gobs, as described in the patent application FR-A-2,735,562 ...), an increase in the liquidus viscosity of said glasses is an appreciable advantage, in terms of lowering the percentage of losses (of rejects, due to the devitrification) and of flexibility of shaping.
- the present invention offers, as indicated above, an improvement of the teaching of the patent US-A-5,070,045 (a teaching according to which, from a single glass of the type specified, glass-ceramics can be obtained rapidly, the predominant crystalline phase of which is a solid solution of ⁇ -quartz or of ⁇ -spodumene, and the linear thermal dilation coefficient of which is very low, even zero), an improvement which aims to minimize the rejects mentioned above.
- Said improvement is based on the incorporation of novel mineral glasses (or novel mineral fillers), which possess a maximum liquidus viscosity. Within them, much less faults are generated during said second step (of conjugated cooling and shaping).
- the present invention offers a command of said second step, which is much greater than that which the prior art offered, without the third step, of ceramming, being disturbed by it.
- Said novel glasses of the invention can be converted into glass-ceramics in a short time (less than two hours), in deforming very little, just as those described in the patent US-A-5,070,045 . They possess, with respect to said glasses of said US patent, a liquidus viscosity which is significantly increased.
- the cerammable glasses which are the starting material, have the composition by weight below (%) : SiO 2 65 - 70 Al 2 O 3 18 - 19.8 Li 2 O 2.5 - 3.8 MgO 0.55 -1.5 ZnO 1.2 - 2.8 BaO 0 - 1.4 SrO 0 - 1.4 with BaO + SrO 0.4 - 1.4 with MgO + BaO + SrO 1.1 - 2.3 As 2 O 3 0 - 1.5 Sb 2 O 3 0 - 1.5 with As 2 O 3 + Sb 2 O 3 0.5 - 1.5 Na 2 O 0 - ⁇ 1 K 2 O 0 - ⁇ 1 with Na 2 O + K 2 O 0 - ⁇ 1 with (2.8 Li 2 O + 1.2 ZnO)/5.2 MgO > 1.8 TiO 2 1.8 - 3.2 ZrO
- Said glasses have a liquidus viscosity which is greater than 700 Pa.s (certainly greater than or equal to 600 Pa.s) and can be thermally crystallized into a glass-ceramic the predominant crystalline phase of which is a solid solution of ⁇ -quartz or of ⁇ -spodumene, and the coefficient of linear thermal dilation of which (20°-700°C) is 0 ⁇ 3 x 10 -7 K -1 .
- Said glasses contain TiO 2 and ZrO 2 , as nucleation agents, which are active in the third step of ceramming set forth above (specified in said US patent), in the amounts mentioned above.
- R ⁇ TiO 2 ZrO 2
- the present invention thus relates to mineral glasses which have a composition by weight (expressed in percentages of oxides), which essentially consists of : SiO 2 65 - 70 Al 2 O 3 18 - 20.5 Li 2 O 2.5 - 3.8 MgO 0.55 -1.5 ZnO 1.2 - 2.8 BaO 0 - 1.4 SrO 0 - 1.4 with BaO + SrO 0.4 - 1.4 with MgO + BaO + SrO 1.1 - 2.3 Na 2 O 0 - ⁇ 1 K 2 O 0 - ⁇ 1 with Na 2 O + K 2 O 0 - ⁇ 1 with (2.8 Li 2 O + 1.2 ZnO)/5.2 MgO > 1.8 TiO 2 1.8 - 3.5 ZrO 2 0.8 - 2.5 with 2.2 ⁇ TiO 2 ZrO 2 ⁇ 4.5 , a ⁇ n ⁇ d optionally at least one fining agent ⁇ 2.
- Said mineral glasses of the invention are virtually glasses according to the patent US-A-5,070,045 . Reference can be made, as already indicated, to the teaching of this US patent, in order notably to have precisions on the respective incorporation amounts of each one of the constituent elements (of said glasses) listed above.
- the glass obtained exhibits an interesting liquidus temperature, which is 50 to 100°C lower than that of the glasses according to the patent US-A-5,070,045 .
- the viscosity of the novel glasses of the invention being comparable to that of the glasses according to said patent US-A-5,070,045 , the gain in the liquidus viscosity is significant.
- R ⁇ TiO 2 ZrO 2 , is kept at less than 4.5, since, over this, it is difficult to obtain glass-ceramics, the predominant crystalline phase of which is a solid solution of ⁇ -quartz, which are transparent. They become opalescent.
- said weight ratio R is between 2.3 and 4.5.
- the mineral glasses of the invention contain, advantageously, an effective, non-excess amount of at least one fining agent.
- the person skilled in the art knows perfectly well how to manage the incorporation of this type of compound within a mineral glass. It is in fact incorporated at less than 2 % by weight of this type of compound within the glasses of the invention.
- the mineral glasses of the invention can also contain AS 2 O 3 and/or Sb 2 O 3 as fining agents, as do the glasses according to the patent US 5,070,045 , in the amounts indicated in said US patent, namely : As 2 O 3 0 - 1.5 Sb 2 O 3 0 - 1.5 with As 2 O 3 + Sb 2 O 3 0.5 - 1.5 (% by weight).
- Said mineral glasses of the invention can, in the same manner, contain other compounds such as SnO 2 , CeO 2 and CI, as fining agents.
- the mineral glasses of the invention can be colored or non-colored.
- coloring agent(s) is (are) in general selected from CoO, Cr 2 O 3 , Fe 2 O 3 , MnO 2 , NiO, V 2 O 5 , CeO 2 (and their mixtures).
- colored mineral glasses of the invention those are more particularly preferred which have the composition by weight indicated above with, in addition, from 0.03 (advantageously 0.05) to 1 % by weight of V 2 O 5 and the condition below : 3.8 % ⁇ TiO 2 + ZrO 2 + 5 ⁇ V 2 ⁇ O 5 ⁇ 6 % .
- Articles notably transparent, black glass-ceramic articles, the main crystalline phase of which is ⁇ -quartz, can be obtained from such glasses of the invention.
- vanadium oxide has a coloring effect which is more marked than within the glasses according to the patent US-A-5,070,045 and, that consequently, lower amounts prove a priori to be sufficient to obtain an equivalent coloration.
- glasses of the invention can have a slight coloration, due to the presence within them of a certain type of impurity(ies).
- the glasses of the invention which do not contain such an effective amount of coloring agent(s) (coloring agent(s) which is (are) added on purpose in their composition) advantageously have a content of alumina (Al 2 O 3 ) of between 19.8 and 20.5 % and a content of zirconium oxide (ZrO 2 ) of between 1.2 and 2.5 %. With such glasses, very transparent glass-ceramics have been obtained, which are without opalescence.
- Transparent, colorless or opalescent glass-ceramic articles, even opaque, colorless glass-ceramic articles, the main crystalline phases of which are ⁇ -quartz or ⁇ -spodumene, respectively, can be obtained from non-colored glasses of the invention.
- transparent, colored or opalescent glass-ceramic articles even opaque, colored glass-ceramic articles, the main crystalline phase of which are ⁇ -quartz or ⁇ -spodumene, respectively, can be obtained from colored glasses of the invention.
- the mineral glasses of the invention can contain other constituents. Obviously, they contain such other constituents only in a limited amount (generally of less than 2 % by weight), only in an amount which does not jeopardize the characteristics of said glasses of the invention. It is thus for example in no way excluded that the glasses of the invention contain P 2 O 5 and/or B 2 O 3 .
- the present invention relates to the use of the mineral glasses above for the preparation of glass-ceramic articles.
- said second object covers the use of fillers which are precursors of said mineral glasses of the invention, for the preparation of glass-ceramic articles.
- the basic glass is isolated or not.
- the glass-ceramic article, obtained by the preparative process above is colorless.
- steps a) to g), clarified above, with a different temperature interval of 1,050-1,200°C (instead of 900-980°C) for the steps e) and f), are carried out in essentially the same manner.
- the ceramming carried out at a higher temperature, leads to the conversion of the transparent crystalline phase of solid solution of ⁇ -quartz (mainly) into another crystalline phase, derived from silica : a crystalline phase of solid solution of ⁇ -spodumene (mainly), which confers to the material an opalescent, white appearance, even an opaque appearance.
- the white color of said material which is more or less opaque, can be sought after in specific domains of application.
- Steps b) to f) of the processes above, of obtaining a glass-ceramic article are advantageously carried out in 2 hours at the maximum, and in about 1 hour in a particularly preferred manner.
- the present invention relates to the glass-ceramic articles, which are obtainable according to the processes specified above, from mineral glasses (or mineral fillers, which are precursors of such glasses) which are constituents of the first object of said invention.
- the glass-ceramic of said articles has the composition indicated above for said mineral glasses.
- Such articles can notably consist of cooktop plates, which are adapted to different types of cooking (resistant, inductive, halogen heating...), of cookware, which are also adapted to different types of cooking, of microwave oven bottom trays, of woodstove windows, of fire protection doors, of fire protection windows. This list is obviously not limitative.
- Examples 1 to 4 and 4' illustrate said invention, and the importance of the invention emerges from the consideration of Examples A, B and C.
- the glasses are prepared in a usual manner from oxides and/or from compounds which are easily decomposable, such as nitrates or carbonates.
- the starting materials are mixed in order to obtain a homogeneous mixture.
- the melted glass is then poured onto a table and is rolled to a thickness of about 6 mm. It is then re-heated for 1 hour at 650°C, and then cerammed according to the following program :
- the liquidus temperatures were determined from small amounts of glass (a few grams), re-molten in platinum crucibles, and then held for 17 hours at the temperature studied before being tempered in air. The liquidus temperature is the lowest plateau temperature after which no crystals are observed.
- Example 1 The transmissions were measured on polished samples of 3 mm thickness. The measurement of visible transmission was made with the illuminant C, at a rate of a measurement point every nm, between 360 and 830 nm. Table 1 A B C Example 1 Example 2 Example 3 Example 4 1.
- the resulting glass-ceramic contains ⁇ -spodumene as main phase. It has a white appearance, slightly translucent. Its dilatation is of 8x10 -7 K -1 (20 - 700°C).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Electric Ovens (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
Description
- The present invention relates to :
- novel mineral glasses which are cerammable ;
- the use of said glasses or of mineral fillers, which are precursors of such glasses, for preparing glass-ceramic articles. In this, said cerammable mineral glasses of the invention are particularly interesting. They enable quality glass-ceramics to be obtained under efficient process conditions ;
- the preparation of glass-ceramic articles, from such glasses or mineral fillers, which are precursors of such glasses ;
- said glass-ceramic articles.
- German patent application
DE 199 39 787 discloses transparent, arsenic and antimony-free glass-ceramics. The light transmission of these glass-ceramics can be adjusted by a combination of vanadium oxide with a solid, liquid and/or gaseous reducing agent, which is added to the glass melt. International patent applicationWO 99/06334 -
US patent 5 931 152 discloses glass-ceramic cooking plates showing a specific geometry. - The present invention is clearly situated along the lines of the teaching of the patent
US-A-5,070,045 . - The present invention offers an improvement of said teaching.
- Said present invention is clearly situated in the general context of the preparation of glass-ceramic articles. It is well-known that this preparation is based on three main process steps :
- melting a mineral glass or melting a mineral filler, which is a precursor of a mineral glass, containing an effective amount of nucleation agent(s). Mention can in general be made of a first step of melting vitrifiable starting materials containing said nucleation agent(s) ;
- cooling and shaping the molten glass obtained, cooling to a temperature which is lower than the conversion domain (interval) of said glass ;
- crystallizing or ceramming the shaped glass by an appropriate heat treatment. In general, this third and last step of the process is carried out in two phases. The shaped glass (the glass article obtained after the second step of the process) is first of all brought to a temperature which is slightly higher than the conversion domain of said glass, so as to generate nucleation grains within it. The temperature is then increased up to a value which is high enough in order that the growth of the crystals on the grains be produced.
- During the second of said steps (cooling and shaping of the melted glass), it is desired to prevent any devitrification, any crystallization, which is synonymous with appearance of faults in the glass prepared.
- On the contrary, during the third of said steps (ceramming), it is desired to crystallize said glass in a controlled manner in order to convert it into a glass-ceramic.
- The characteristics of devitrification of the glass, in particular its liquidus viscosity, are critical during the second of said steps. It is known that a risk is taken of generating rejects - glass having devitrification faults, within its mass and/or on the surface - insofar as the viscosity of the glass in question is, during shaping, higher than its liquidus viscosity. Each shaping process necessitates that the glass be conditioned in a given viscosity range. A glass having a higher liquidus viscosity enables an easier shaping. The tolerance with respect to the existence of cold points is greater. This is all the more true because the volume of glass concerned is greater.
- In the case of the glass-ceramics, the objects formed (cooktop plates, fire protection windows...) are in general of quite large dimensions, and, whatever the shaping technique implemented for the shaping of the precursor glasses be (lamination, pressing or shaping from gobs, as described in the patent application
FR-A-2,735,562 - The present invention offers, as indicated above, an improvement of the teaching of the patent
US-A-5,070,045 (a teaching according to which, from a single glass of the type specified, glass-ceramics can be obtained rapidly, the predominant crystalline phase of which is a solid solution of β-quartz or of β-spodumene, and the linear thermal dilation coefficient of which is very low, even zero), an improvement which aims to minimize the rejects mentioned above. Said improvement is based on the incorporation of novel mineral glasses (or novel mineral fillers), which possess a maximum liquidus viscosity. Within them, much less faults are generated during said second step (of conjugated cooling and shaping). In an entirely surprising way, the present invention offers a command of said second step, which is much greater than that which the prior art offered, without the third step, of ceramming, being disturbed by it. - Said novel glasses of the invention can be converted into glass-ceramics in a short time (less than two hours), in deforming very little, just as those described in the patent
US-A-5,070,045 . They possess, with respect to said glasses of said US patent, a liquidus viscosity which is significantly increased. - The following can be specified with reference to the prior art.
- For many years, with reference to the third step of ceramming, and only with reference to said third step, the importance is known of incorporating, in combination, the nucleation agents TiO2 and ZrO2. On this subject, reference can be made to the article by D.R. Stewart entitled "TiO2 and ZrO2 as nucleants in a lithia aluminosilicate glass-ceramic" (pages 83-90 of "Advances in Nucleation and Crystallization in Glasses. Edited by L.L. Hench and S.W. Freiman. American Ceramic Society, Columbus, OH, 1971"). Said article explains the interest in incorporating said nucleating agents, TiO2 and ZrO2, in a molar ratio,
- In the patent
US-A-5,070,045 , the preparation, under advantageous conditions, notably in terms of rapidity, of glass-ceramic articles, is thus described. The cerammable glasses which are the starting material, have the composition by weight below (%) :SiO2 65 - 70 Al2O3 18 - 19.8 Li2O 2.5 - 3.8 MgO 0.55 -1.5 ZnO 1.2 - 2.8 BaO 0 - 1.4 SrO 0 - 1.4 with BaO + SrO 0.4 - 1.4 with MgO + BaO + SrO 1.1 - 2.3 As2O3 0 - 1.5 Sb2O3 0 - 1.5 with As2O3 + Sb2O3 0.5 - 1.5 Na2O 0 - < 1 K2O 0 - < 1 with Na2O + K2O 0 - < 1 with (2.8 Li2O + 1.2 ZnO)/5.2 MgO > 1.8 TiO2 1.8 - 3.2 ZrO2 1 - 2.5. - Said glasses have a liquidus viscosity which is greater than 700 Pa.s (certainly greater than or equal to 600 Pa.s) and can be thermally crystallized into a glass-ceramic the predominant crystalline phase of which is a solid solution of β-quartz or of β-spodumene, and the coefficient of linear thermal dilation of which (20°-700°C) is 0 ± 3 x 10-7 K-1.
- Said glasses contain TiO2 and ZrO2, as nucleation agents, which are active in the third step of ceramming set forth above (specified in said US patent), in the amounts mentioned above. With reference to Tables 1 and 2 of said US patent, it is noted that the weight ratio
- In this US patent, no teaching is anyway provided on any incidence of said weight ratio (molar ratio) in the implementation of the second step of cooling and shaping set forth above (also specified in said US patent).
-
- According to a first object, the present invention thus relates to mineral glasses which have a composition by weight (expressed in percentages of oxides), which essentially consists of :
SiO2 65 - 70 Al2O3 18 - 20.5 Li2O 2.5 - 3.8 MgO 0.55 -1.5 ZnO 1.2 - 2.8 BaO 0 - 1.4 SrO 0 - 1.4 with BaO + SrO 0.4 - 1.4 with MgO + BaO + SrO 1.1 - 2.3 Na2O 0 - < 1 K2O 0 - < 1 with Na2O + K2O 0 - < 1 with (2.8 Li2O + 1.2 ZnO)/5.2 MgO > 1.8 TiO2 1.8 - 3.5 ZrO2 0.8 - 2.5 with optionally at least one fining agent < 2. - Said mineral glasses of the invention are virtually glasses according to the patent
US-A-5,070,045 . Reference can be made, as already indicated, to the teaching of this US patent, in order notably to have precisions on the respective incorporation amounts of each one of the constituent elements (of said glasses) listed above. - With reference to the amount of incorporation of Al2O3, it is noted that within the glasses of the invention, it has proved to be possible, even advantageous, that it be greater than 19.8 %. This value of 19.8 % was the critical high value given in the patent
US-A-5,070,045 . In incorporating more Al2O3 within the glasses of the invention, glass-ceramics have been obtained from said glasses, which have a better transparency. -
-
- The glass obtained exhibits an interesting liquidus temperature, which is 50 to 100°C lower than that of the glasses according to the patent
US-A-5,070,045 . The viscosity of the novel glasses of the invention being comparable to that of the glasses according to said patentUS-A-5,070,045 , the gain in the liquidus viscosity is significant. -
- According to an advantageous variant, said weight ratio R is between 2.3 and 4.5.
- The mineral glasses of the invention contain, advantageously, an effective, non-excess amount of at least one fining agent. The person skilled in the art knows perfectly well how to manage the incorporation of this type of compound within a mineral glass. It is in fact incorporated at less than 2 % by weight of this type of compound within the glasses of the invention.
- As an illustration, and in a manner which is in no way limiting, an indication is made that the mineral glasses of the invention can also contain AS2O3 and/or Sb2O3 as fining agents, as do the glasses according to the patent
US 5,070,045 , in the amounts indicated in said US patent, namely :As2O3 0 - 1.5 Sb2O3 0 - 1.5 with As2O3 + Sb2O3 0.5 - 1.5 (% by weight). - Said mineral glasses of the invention can, in the same manner, contain other compounds such as SnO2, CeO2 and CI, as fining agents.
- The mineral glasses of the invention can be colored or non-colored.
- In order that they display a real coloration, they contain, in addition to the constituent elements listed above, an effective amount of at least one coloring agent. Said coloring agent(s) is (are) in general selected from CoO, Cr2O3, Fe2O3, MnO2, NiO, V2O5, CeO2 (and their mixtures).
-
- Articles, notably transparent, black glass-ceramic articles, the main crystalline phase of which is β-quartz, can be obtained from such glasses of the invention.
- It was observed that within such glasses of the invention, vanadium oxide has a coloring effect which is more marked than within the glasses according to the patent
US-A-5,070,045 and, that consequently, lower amounts prove a priori to be sufficient to obtain an equivalent coloration. - Without containing an effective amount of coloring agent(s), as specified above, glasses of the invention can have a slight coloration, due to the presence within them of a certain type of impurity(ies).
- The glasses of the invention, which do not contain such an effective amount of coloring agent(s) (coloring agent(s) which is (are) added on purpose in their composition) advantageously have a content of alumina (Al2O3) of between 19.8 and 20.5 % and a content of zirconium oxide (ZrO2) of between 1.2 and 2.5 %. With such glasses, very transparent glass-ceramics have been obtained, which are without opalescence.
- Transparent, colorless or opalescent glass-ceramic articles, even opaque, colorless glass-ceramic articles, the main crystalline phases of which are β-quartz or β-spodumene, respectively, can be obtained from non-colored glasses of the invention.
- In the same way, transparent, colored or opalescent glass-ceramic articles, even opaque, colored glass-ceramic articles, the main crystalline phase of which are β-quartz or β-spodumene, respectively, can be obtained from colored glasses of the invention.
- In addition to the essential and optional constituents set forth above, the mineral glasses of the invention can contain other constituents. Obviously, they contain such other constituents only in a limited amount (generally of less than 2 % by weight), only in an amount which does not jeopardize the characteristics of said glasses of the invention. It is thus for example in no way excluded that the glasses of the invention contain P2O5 and/or B2O3.
- According to its second object, the present invention relates to the use of the mineral glasses above for the preparation of glass-ceramic articles. In an entirely logical way, said second object covers the use of fillers which are precursors of said mineral glasses of the invention, for the preparation of glass-ceramic articles. In fact, according to the exact method of implementation of this preparation, the basic glass is isolated or not.
- Said preparation of glass-ceramic articles, which constitutes the third object of the present invention, is implemented (almost) as described in the patent
US-A-5,070,045 , with the original starting material described above (the composition of which, which is characterized mainly by - Thus, in order to prepare a glass-ceramic article containing a solid solution of β-quartz as predominant crystalline phase, the steps below are essentially carried out :
- a) melting a glass as described above or melting a filler which is a precursor of a glass as described above ;
- b) cooling the melted glass obtained to a temperature of lower than its conversion interval and simultaneously shaping it into the shape of the final article sought after ;
- c) increasing the temperature of the glass shape obtained, at the rate of 50 to 80°C/minute up to a temperature in the range 670-800°C ;
- d) keeping said glass article within this temperature range between 670 and 800°C, for 15 to 25 minutes, in order to develop grains or nuclei within it ;
- e) increasing the temperature of said glass article, which is now nucleated, at a rate sufficient, in order to bring it, in 15 - 30 minutes, into the temperature interval of 900 - 980°C (it proved to be possible, even advantageous, to increase said temperature up to 980°C) ;
- f) keeping said nucleated glass article in this temperature interval of 900 - 980°C, for 10 to 25 minutes, so as to make crystals of solid solution of β-quartz grow on these grains or nuclei ;
- g) rapidly cooling the crystallized article to ambient temperature.
- Without incorporating an effective amount of at least one coloring agent in the composition of the initial glass (of the initial filler), and in the absence of colorant impurety(ies), the glass-ceramic article, obtained by the preparative process above, is colorless.
- For the preparation of a glass-ceramic article containing a solid solution of β-spodumene as predominant crystalline phase, steps a) to g), clarified above, with a different temperature interval of 1,050-1,200°C (instead of 900-980°C) for the steps e) and f), are carried out in essentially the same manner.
- The ceramming, carried out at a higher temperature, leads to the conversion of the transparent crystalline phase of solid solution of β-quartz (mainly) into another crystalline phase, derived from silica : a crystalline phase of solid solution of β-spodumene (mainly), which confers to the material an opalescent, white appearance, even an opaque appearance. The white color of said material, which is more or less opaque, can be sought after in specific domains of application.
- For the preparation of a colored glass-ceramic article, containing a solution of β-quartz or of β-spodumene as predominant crystalline phase, the processes specified above are implemented, in incorporating, in step a), an effective amount of at least one coloring agent. It is recalled :
- that the coloring agent(s) being incorporated is (are) generally selected from CoO, Cr2O3, Fe2O3, MnO2, NiO, V2O5, Ce2O (and the mixtures of these oxides) ;
- that 0.03 to 1 % (very advantageously 0.05 to 1 %) by weight of V2O5 is advantageously incorporated with the condition below: 3.8 % ≤ TiO2 + ZrO2 + 5V2O5 ≤ 6 %.
- Steps b) to f) of the processes above, of obtaining a glass-ceramic article, are advantageously carried out in 2 hours at the maximum, and in about 1 hour in a particularly preferred manner.
- According to its last object, the present invention relates to the glass-ceramic articles, which are obtainable according to the processes specified above, from mineral glasses (or mineral fillers, which are precursors of such glasses) which are constituents of the first object of said invention. The glass-ceramic of said articles has the composition indicated above for said mineral glasses. Such articles can notably consist of cooktop plates, which are adapted to different types of cooking (resistant, inductive, halogen heating...), of cookware, which are also adapted to different types of cooking, of microwave oven bottom trays, of woodstove windows, of fire protection doors, of fire protection windows. This list is obviously not limitative.
- The invention is now illustrated by the Examples below. More specifically, Examples 1 to 4 and 4' illustrate said invention, and the importance of the invention emerges from the consideration of Examples A, B and C. Said Examples A and B illustrate the prior art (R ≤ 2) whereas said Example C illustrates a specific case wherein R > 4.5 (
- Table 1 below indicates,
- in its first part, the compositions by weight of the glasses in question and their liquidus characteristics ;
- in its second part, the characteristics of glass-ceramics obtained from said glasses ; said glass-ceramics containing a solution of β-quartz as predominant crystalline phase.
- For each example, an indication is made, in said Table 1, of the weight ratios
US-A-5,070,045 , said ratio R' is of the order of 2.4. - The glasses are prepared in a usual manner from oxides and/or from compounds which are easily decomposable, such as nitrates or carbonates. The starting materials are mixed in order to obtain a homogeneous mixture. About 1,000 g, placed in a platinum crucible, are molten in an electric oven for 10 hours at 1,650°C. The melted glass is then poured onto a table and is rolled to a thickness of about 6 mm. It is then re-heated for 1 hour at 650°C, and then cerammed according to the following program :
- rapid rise to 670°C,
- rise from 670 to 800°C (nucleation interval) in 24 minutes,
- rise, over 20 minutes, from 800 to 900°C,
- upkeep for 15 minutes between 900 and 980°C (growth interval),
- rapid cooling.
- The liquidus temperatures were determined from small amounts of glass (a few grams), re-molten in platinum crucibles, and then held for 17 hours at the temperature studied before being tempered in air. The liquidus temperature is the lowest plateau temperature after which no crystals are observed.
- The transmissions were measured on polished samples of 3 mm thickness. The measurement of visible transmission was made with the illuminant C, at a rate of a measurement point every nm, between 360 and 830 nm.
Table 1 A B C Example 1 Example 2 Example 3 Example 4 1. Composition (% by weight) SiO2 68.8 67.6 68.5 68.4 68.5 67.6 67.4 Al2O3 18.95 19.85 18.95 18.95 18.95 19.75 20 Li2O 3.45 3.45 3.45 3.45 3.45 3.45 3.45 MgO 1.2 1.22 1.2 1.2 1.2 1.2 1.2 ZnO 1.62 1.66 1.62 1.62 1.62 1.62 1.62 BaO 0.8 0.8 0.8 0.8 0.8 0.8 0.8 MgO+BaO+SrO 2 2.02 2 2 2 2 2 As2O3 0.5 0.79 0.8 0.8 0.8 0.8 0.8 Sb2O3 As2O3+Sb2O3 0.5 0.79 0.8 0.8 0.8 0.8 0.8 Na2O 0.15 0.17 0.15 0.15 0.15 0.15 0.17 K2O 0.2 0.19 0.2 0.2 0.2 0.2 0.19 Na2O+K2O 0.35 0.36 035 0.35 0.35 0.35 0.36 (2.8Li2O+1.2ZnO)/5.2MgO 1.86 1.84 1.86 1.86 1.86 1.86 1.86 TiO2 2.6 2.6 3.8 3.1 3.3 3.1 3.1 ZrO2 1.7 1.68 0.5 1.3 1 1.3 1.3 R = TiO2/ZrO2 (weight ratio) 1.53 1.55 7.6 2.38 3.3 2.38 2.38 R1 = TiO2/ZrO2 (molar ratio) 2.4 2.4 11.7 3.6 5.1 3.7 3.7 V2O5 0.22 0.02 0.1 0.09 0.1 2. Liquidus 1,350°C 1,350°C 1,300°C 1,250°C 1,300°C 1,300°C 6,000 P 6,000 P > 30,000 P 10,000 P 30,000 P 10,000 P 10,000 P 3. Appearance after ceramming transparent black color transparent practically colorless Strongly opalescent black color transparent black color transparent black color transparent black color transparent practically colorless 4. Properties after ceramming : Dilatation (25-700°C) -1x10-7K-1 -1x10-7K-1 -0.3x10-7K-1 0.2x10-7K-1 -0.1x10-7K-1 Visible transmission 5.65 4 2.3 4.5 Transmission at 1,000 nm 71.9 70.1 71.3 72.9 Transmission at 2,000 nm 79.8 82.5 82.9 82.5 - Glass of Example 4 underwent the following heat treatment :
- rapid rise to 670°C,
- rise from 670 to 800°C (nucleation interval) in 20 minutes,
- rise in 30 minutes to 1,070°C,
- upkeep for 30 minutes at 1,070°C,
- rapid cooling.
- The resulting glass-ceramic contains β-spodumene as main phase. It has a white appearance, slightly translucent. Its dilatation is of 8x10-7K-1 (20 - 700°C).
Claims (12)
- A mineral glass having a composition, expressed in percentages by weight of oxides, which essentially consists of :
SiO2 65 - 70 Al2O3 18 - 20.5 Li2O 2.5 - 3.8 MgO 0.55 -1.5 ZnO 1.2 - 2.8 BaO 0 - 1.4 SrO 0 - 1.4 with BaO + SrO 0.4 - 1.4 with MgO + BaO + SrO 1.1 - 2.3 Na2O 0 - < 1 K2O 0 - < 1 with Na2O + K2O 0 - < 1 with (2.8 Li2O + 1.2 ZnO)/5.2 MgO > 1.8 TiO2 1.8 - 3.5 ZrO2 0.8 - 2.5 with advantageously optionally at least one fining agent < 2. - The mineral glass according to claim 1, the composition of which further contains an effective amount of at least one coloring agent selected from CoO, Cr2O3, Fe2O3, MnO2, NiO, V2O5 and CeO2.
- The mineral glass according to one of claims 1 or 2, the composition of which further contains 0.03 to 1 % by weight of V2O5 with 3.8 % ≤ TiO2 + ZrO2 + 5V2O5 ≤ 6 %.
- The mineral glass according to claim 1, the composition of which does not further contain any coloring agent, the content of which of Al2O3 is between 19.8 and 20.5 % and the content of which of ZrO2 is between 1.2 and 2.5 %.
- Use of a mineral glass according to any one of the preceeding claims, or of a filler which is a precursor of a mineral glass according to any one of the preceding claims, for the preparation of a glass-ceramic article.
- A process for preparing a glass-ceramic article containing a solution of ß-quartz as predominant crystalline phase, characterised in that it essentially comprises the following successive steps :a) melting a glass according to any one of claims 1 to 4, or melting a filler which is a precursor of a glass according to any one of claims 1to 4;b) cooling the melted glass obtained to a temperature of lower than its conversion interval and simultaneously shaping it into the shape of the final article sought after ;c) increasing the temperature of the glass shape obtained, at a rate of 50 to 80°C/min up to a temperature in the range 670 - 800°C ;d) keeping said glass article within this temperature range between 670 and 800°C, for 15 to 25 min, in order to develop grains or nuclei within it ;e) increasing the temperature of said glass article, which is now nucleated, at a rate sufficient in order to bring it in 15 - 30 min, into the temperature interval of 900 - 980°C ;f) keeping said nucleated glass article in this temperature interval of 900 - 980°C, for 10 to 25 min, so as to make the crystals of β-quartz solid solution grow on these grains or nuclei ;g) rapidly cooling the crystallised article to ambient temperature.
- A process for preparing a glass-ceramic article containing a solid solution of β-spodumene as predominant crystalline phase, characterised in that it essentially comprises the successive steps a) to g) of the process according to claim 6, with a temperature interval of 1,050-1,200°C, for said steps e) and f).
- A process for preparing a colored glass-ceramic article, characterised in that it comprises implementing steps a) to g) of the process according to claim 6 or claim 7, the glass or the glass filler being incorporated in step a) further containing an effective amount of at least one coloring agent selected from CoO, Cr2O3, Fe2O3, MnO2, NiO, V2O5 and CeO2.
- The process according to any one of claims 6 to 9, characterised in that the total duration for implementing steps b) to f) does not exceed about 2 hours, and is advantageously about 1 hour.
- A glass-ceramic article, obtainable according to the process according to any one of claims 6 to 10, the glass-ceramic of which has a composition, expressed in percentages by weight of oxides, which essentially consists of :
SiO2 65 - 70 Al2O3 18 - 20.5 Li2O 2.5 - 3.8 MgO 0.55 -1.5 ZnO 1.2 - 2.8 BaO 0 - 1.4 SrO 0 - 1.4 with BaO + SrO 0.4 - 1.4 with MgO + BaO + SrO 1.1 - 2.3 Na2O 0 - < 1 K2O 0 - < 1 with Na2O + K2O 0 - < 1 with (2.8 Li2O + 1.2 ZnO)/5.2 MgO > 1.8 TiO2 1.8 - 3.5 ZrO2 0.8 - 2.5 with advantageously optionally at least one fining agent < 2. - The article according to claim 11, consisting of a cooktop plate, a cookware, a microwave oven bottom tray, a woodstove window, a fire protection door, or a fire protection window.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0211221 | 2002-09-11 | ||
FR0211221A FR2844261B1 (en) | 2002-09-11 | 2002-09-11 | CERAMIZABLE MINERAL GLASS, MANUFACTURE OF VITROCERAMIC ARTICLES, THE SAID ARTICLES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1398303A1 EP1398303A1 (en) | 2004-03-17 |
EP1398303B1 true EP1398303B1 (en) | 2015-11-11 |
Family
ID=31725990
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03292222.1A Expired - Fee Related EP1398303B1 (en) | 2002-09-11 | 2003-09-10 | Cerammable mineral glass, preparation of glass-ceramic articles, said articles |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1398303B1 (en) |
JP (1) | JP4471075B2 (en) |
CN (1) | CN100349816C (en) |
FR (1) | FR2844261B1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE202018102514U1 (en) | 2017-12-22 | 2018-05-22 | Schott Ag | Glass-ceramic with reduced lithium content |
US11306021B2 (en) | 2018-11-26 | 2022-04-19 | Owens Coming Intellectual Capital, LLC | High performance fiberglass composition with improved elastic modulus |
US11524918B2 (en) | 2018-11-26 | 2022-12-13 | Owens Corning Intellectual Capital, Llc | High performance fiberglass composition with improved specific modulus |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2887870B1 (en) | 2005-06-30 | 2007-10-05 | Snc Eurokera Soc En Nom Collec | PREPARATION OF BETA-QUARTZ AND / OR BETA-SPODUMENE VITROCERAMICS, ARTICLES IN SUCH VITROCERAMICS; VITROCERAMICS, ARCTICLES IN SAID VITROCERAMIC AND PRECURSOR GLASSES |
FR2887871B1 (en) * | 2005-06-30 | 2007-10-12 | Snc Eurokera Soc En Nom Collec | BETA-QUARTZ AND / OR BETA SPODUMENE VITROCERAMICS, PRECURSOR GLASSES, ARTICLES THEREOF, VITROCERAMIC PRODUCTS AND ARTICLES |
FR2902421B1 (en) * | 2005-12-07 | 2008-11-07 | Snc Eurokera Soc En Nom Collec | QUARTZ AND / OR B SPODUMENE GLASS VITROCERAMICS, PRECURSOR GLASSES, ARTICLES THEREOF, VITROCERAMIC VITROCERAMIC PRODUCTS AND ARTICLES THEREOF |
US7456121B2 (en) | 2006-06-23 | 2008-11-25 | Eurokera | Glass-ceramic materials, precursor glass thereof and process-for making the same |
US8127571B2 (en) * | 2006-10-27 | 2012-03-06 | Eurokera S.N.C. | Method of refining a lithium aluminosilicate glass and glass-ceramic obtained |
FR2946041B1 (en) * | 2009-05-29 | 2012-12-21 | Eurokera | VITROCERAMIC AND ARTICLES IN VITROCERAMIC, IN PARTICULAR COOKING PLATES, COLORED |
FR2998294B1 (en) * | 2012-11-22 | 2014-12-19 | Eurokera | QUARTZ-BETA VITROCERAMICS WITH CONTROLLED TRANSMISSION CURVE AND HIGH IRON OXIDE AND TIN OXIDE CONTENT; ARTICLES IN VITROCERAMIC LENSES, PRECURSOR GLASSES |
CN103058524B (en) * | 2013-01-06 | 2014-07-16 | 浙江长兴诺万特克玻璃有限公司 | Arsenic-free low-expansion black and transparent microcrystalline glass |
FR3020359B1 (en) * | 2014-04-29 | 2016-05-06 | Eurokera | PARTIALLY CRYSTALLIZED GLASS PLATE |
CN105948508B (en) * | 2016-04-25 | 2018-05-01 | 四川一名微晶科技股份有限公司 | It is devitrified glass that raw material is produced using all-electric melting rolling process and preparation method thereof using ferronickel waste residue |
DE102018110897A1 (en) | 2017-12-22 | 2018-06-21 | Schott Ag | Furnishings and equipment for kitchens or laboratories with display devices |
DE102018110910A1 (en) | 2017-12-22 | 2018-06-21 | Schott Ag | Furnishings and fittings for kitchens or laboratories with lighting elements |
DE202018102536U1 (en) | 2017-12-22 | 2018-05-22 | Schott Ag | Cover plate with neutral color coating |
DE102018110908A1 (en) | 2017-12-22 | 2018-06-21 | Schott Ag | Transparent, colored lithium aluminum silicate glass ceramic and method for producing and using the glass ceramic |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999006334A1 (en) * | 1997-08-01 | 1999-02-11 | Eurokera | Glass-ceramic plate and method for making same |
US5931152A (en) * | 1995-06-19 | 1999-08-03 | Eurokera | Glass-ceramic cooking plate for gas cookers, and method for making same |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3926602A (en) * | 1974-06-19 | 1975-12-16 | Corning Glass Works | Glass-ceramic articles with reflective surfaces |
US4018612A (en) * | 1976-03-25 | 1977-04-19 | Corning Glass Works | Transparent beta-quartz glass-ceramics |
US4461839A (en) * | 1982-12-20 | 1984-07-24 | Corning Glass Works | Colored transparent, translucent and opaque glass-ceramics |
FR2657079B1 (en) | 1990-01-12 | 1993-04-09 | Corning France | VITROCERAMIC PRECURSOR GLASSES, PROCESS FOR CONVERTING THESE VERY LOW OR NULL DILATION VITROCERAMIC GLASSES AND VITROCERAMIC MATERIALS OBTAINED. |
EP0997445B1 (en) * | 1998-10-27 | 2004-03-10 | Corning Incorporated | Low expansion glass-ceramics |
DE19939787C2 (en) * | 1999-08-21 | 2003-11-27 | Schott Glas | Transparent glass-ceramic, which can be colored dark with the addition of vanadium oxide, with high-quartz mixed crystals as the predominant crystal phase, process for their production and their use |
-
2002
- 2002-09-11 FR FR0211221A patent/FR2844261B1/en not_active Expired - Fee Related
-
2003
- 2003-09-10 EP EP03292222.1A patent/EP1398303B1/en not_active Expired - Fee Related
- 2003-09-11 CN CNB031593763A patent/CN100349816C/en not_active Expired - Fee Related
- 2003-09-11 JP JP2003319504A patent/JP4471075B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5931152A (en) * | 1995-06-19 | 1999-08-03 | Eurokera | Glass-ceramic cooking plate for gas cookers, and method for making same |
WO1999006334A1 (en) * | 1997-08-01 | 1999-02-11 | Eurokera | Glass-ceramic plate and method for making same |
Non-Patent Citations (1)
Title |
---|
HANS BACH: "Low Thermal Expansion Glass Ceramics", 1995, SPRINGER-VERLAG, ISBN: 3-540-58598-2, article ULRICH SCHIFFNER: "Nucleation in Parent Glasses for Lithia Alumino-Silicate Glass Ceramics", pages: 25 - 38, XP007919675 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE202018102514U1 (en) | 2017-12-22 | 2018-05-22 | Schott Ag | Glass-ceramic with reduced lithium content |
DE102018110855A1 (en) | 2017-12-22 | 2018-06-28 | Schott Ag | Glass-ceramic with reduced lithium content |
EP3502069A1 (en) | 2017-12-22 | 2019-06-26 | Schott Ag | Glass ceramic with reduced lithium content |
US11306021B2 (en) | 2018-11-26 | 2022-04-19 | Owens Coming Intellectual Capital, LLC | High performance fiberglass composition with improved elastic modulus |
US11524918B2 (en) | 2018-11-26 | 2022-12-13 | Owens Corning Intellectual Capital, Llc | High performance fiberglass composition with improved specific modulus |
Also Published As
Publication number | Publication date |
---|---|
EP1398303A1 (en) | 2004-03-17 |
CN100349816C (en) | 2007-11-21 |
FR2844261A1 (en) | 2004-03-12 |
JP2004099436A (en) | 2004-04-02 |
CN1495138A (en) | 2004-05-12 |
JP4471075B2 (en) | 2010-06-02 |
FR2844261B1 (en) | 2006-02-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102631331B1 (en) | Transparent β-quartz glass-ceramic with low lithium content | |
US8759239B2 (en) | Transparent, colorless low-titania β-quartz glass-ceramic material | |
EP3877343B1 (en) | Transparent beta-quartz glass-ceramics with a low lithium content | |
EP1398303B1 (en) | Cerammable mineral glass, preparation of glass-ceramic articles, said articles | |
JP5253409B2 (en) | Transparent, colorless, titania-free, beta, quartz, glass and ceramic materials | |
EP1704125B1 (en) | Glass and glass-ceramic materials, articles and method of preparing the same | |
JP7477644B2 (en) | Transparent beta quartz glass ceramic with specific transmittance | |
EP1899276B1 (en) | PREPARATION OF GLASS-CERAMICS OF ß-QUARTZ AND/OR OF ß-SPODUMENE, OF ARTICLES MADE FROM SUCH GLASS-CERAMICS ; GLASS-CERAMICS, ARTICLES MADE FROM SAID GLASS-CERAMICS AND PRECURSOR GLASSES | |
US7456121B2 (en) | Glass-ceramic materials, precursor glass thereof and process-for making the same | |
EP1901999B1 (en) | GLASS-CERAMICS OF ß-QUARTZ AND/OR ß-SPODUMENE, PRECURSOR GLASSES, ARTICLES MADE FROM SAID GLASS-CERAMICS, PREPARATION OF SAID GLASS-CERAMICS AND ARTICLES | |
EP0536478A1 (en) | Variably translucent glassceramic article and method for making | |
JP2010510952A5 (en) | ||
JP2004075441A (en) | Lithium oxide-alumina-silica-based crystalline glass and crystallized glass, and method of manufacturing the crystalline glass and the crystallized glass | |
US7071131B2 (en) | Cerammable mineral glass, glass-ceramic articles and preparation thereof | |
CA1299590C (en) | Glass-ceramic article, process for its production and thermally crystallizable glass |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
17P | Request for examination filed |
Effective date: 20040906 |
|
AKX | Designation fees paid |
Designated state(s): DE ES FR GB IT |
|
17Q | First examination report despatched |
Effective date: 20050121 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20150421 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAR | Information related to intention to grant a patent recorded |
Free format text: ORIGINAL CODE: EPIDOSNIGR71 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
INTG | Intention to grant announced |
Effective date: 20150923 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE ES FR GB IT |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 60348240 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151111 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151111 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 60348240 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20160812 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160910 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160910 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20210831 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20210812 Year of fee payment: 19 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 60348240 Country of ref document: DE Representative=s name: CBDL PATENTANWAELTE GBR, DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60348240 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220930 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230401 |